Patent Application
20130029884
The present invention relates to biocide formulations, their preparation and their uses including their use in oil and gas exploration and production as well as ore and mineral processing slurries, such as in the production of paper, wood, pulp, and kaolin clay and their products that require control of microorganisms. The biocide formulations can also be used as additives to water-based solutions, such as in latex paints to control undesirable properties such as odor, staining and discoloration due to microorganisms.
As an example of an application, after a well is drilled into a subterranean geological formation that contains oil or natural gas, the well is frequently treated to increase the production of oil and/or natural gas. A well can be drilled vertical until reaching a shale formation containing oil or gas and then drilled horizontal in the shale formation to release the oil or gas. One common treatment is to employ hydraulic fracturing. In hydraulic fracturing a fluid containing mostly water along with friction reducers, proppants (such as sand), biocides, oxygen scavengers, polymers, and other chemicals to prevent corrosion of metal pipes are used. The fluid is pumped at large volumes and under high pressure into the well. The high pressure fluid, which exceeds the strength of the rock or shale formation, will migrate along rock or shale formations which have been opened by the fluid, and create channels in the rock or shale formation. These channels, which can extend for several hundreds of feet, provide additional paths for the oil and/or natural gas to migrate to the well bore hole, thus improving the production of the well. The proppant, which is usually sand, is carried by the fluid into the channels formed and helps to maintain the channel in an open position, once the pressure is reduced and the fluid is partially removed from the well.
The hydraulic fracturing fluids contain a biocide to inhibit the growth of microbes. The biocide used must have several attributes to be successful. The biocide must control the sulfate reducing bacteria (SRB); slime producing bacteria (SPB) and acid producing bacteria (APB) and other microorganisms. The growth of these bacteria can hinder the flow of oil or natural gas through the channels formed by hydraulic fracturing and also cause the natural gas to become “sour.” Sour gas will be required to undergo further treatment before being used in commerce.
The fluid used in hydraulic fracturing can be relatively pure before being pumped down the well. Once the fluid is in contact with the subterrain surface, it can come in contact with various salts found at these extreme depths. Potassium, calcium, barium, magnesium, and sodium salts are common contaminants that the fluids encounter. Thus, the biocide must be effective when salts are present. The biocides must also be effective at elevated temperatures, which can reach temperatures of up to 85° C. and higher. Also, because of the large volume of water used and because the wells are usually in remote locations, the water can be sourced from many sources. Ponds, lakes, and river waters are frequently used and these waters can have various salts and microbes in them.
The biocides used in hydraulic fracturing must not only inhibit the growth of microbes, but also have several other properties. They should be gentle and safe for the environment, the equipment coming in contact with it, and any personnel working with it. They should have extended shelf life, be effective when used under aerobic and anaerobic conditions, active over a wide pH range, non-oxidizing, non-reactive with other chemistries used with it or in association with such applications.
In addition to the hydraulic fracturing fluid, several other water based fluids used in the oil and natural gas drilling and production operation benefit from the use of a biocide. These other fluids include drilling waters, drilling muds, field water systems, flood water for enhanced recovery systems, injection waters, holding pond water, disposal-well water, and water holding tanks. Uses in fields other than the oil and natural gas industries that require a biocide include ore and mineral processing slurries, such as in the manufacture of kaolin (clay). Also, the wood and pulp industry such as the production of paper and other wood products, require a biocide in their processes. Biocides are also used in polymers, films, porous and nonporous structures to prevent the growth of microorganisms which can cause undesirable properties. Generally, biocides can be applied to any water based solution that is vulnerable to microbial contamination.
Several prior art references disclose various biocides for use in oil field applications and mineral slurries.
U.S. Pat. No. 4,552,591 discloses a biocide composition for oil field fluid polymers and oil field water polymers where a biocide is absorbed on the surface of a solid, particulate absorbent and lessens personal and environmental contamination by spilled or splashed liquid biocides. The biocide is a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
U.S. Pat. No. 5,637,587 discloses an antimicrobial composition comprising 1-(3-chloroallyl)-3,5,7 triaza-1-azoniaadamantane chloride and 2-bromo-2-nitropropane-1,3-diol. The reference also provides a method for inhibiting microbial growth in an aqueous mineral ore slurry, e.g., kaolin slurry, by adding a microbicidal composition to the slurry comprising the above mentioned biocides.
U.S. Patent Application 20080032903 discloses a well stimulation and treatment fluid that includes water, a polymer from the group of galactomannan polymers, derivatized glactomannan polymers, starch, xanthan gums, hydroxyl celluloses, polyvinyl alcohol polymers, copolymers of vinyl alcohol and vinyl acetate, and a biocide of 2,5-dimethyl-1,3,5-thiadiazinane-2-thione (Dazomet). Also disclosed is adding an effective amount of 2,5-dimethyl-1,3,5-thiadiazinane-2-thione to the well stimulation fluid.
U.S. Patent Application 20100137168 discloses nanoemulsions useful to the oil fields and more particularly water-in-oil, oil-in-water, and other classes of nanoemulsions found beneficial in drilling, well remediation, and other oil and gas industry related operations. Additionally, nanoemulsions may reduce friction pressure losses, as well as reduce subsidence of solid weight material during oil and gas operations. There is no mention of incorporating a biocide in this application.
The prior art biocides have various shortcomings. Some are rather toxic to personnel handling them or to the environment. Others do not work well in the presence of high salt concentrations or at higher temperatures. Still others are corrosive to equipment or interfere with other chemistries used in oil and gas production. Still others are so reactive that they have limited use life.
Some prior art biocides and their shortcomings are discussed below. The biocide 2,5-dimethyl-1,3,5-thiadiazinane-2-thione (referred to as ICI 3240 or Dazamet) is supplied at a pH of 12-14 and has a hydrolysis half life of 0.15 days. Glutaraldehyde, known for its fixative/crosslinking properties is a known toxin and of environmental concern, can have a deleterious affect on the fluid viscosity. Tetrakis hydroxylmethyl phosphonium sulfate (THPS) is toxic category 1 (toxic) at 20% concentrations, requires an activation step to release formaldehyde (a known carcinogen), has been found to interact with the polymer and limit viscosity development when added pre-inversion and post-inversion, and has demonstrated metabolism under only anaerobic conditions. Dibromocyanoacetamide (DBNPA) degrades to ammonia and bromide ion, in the liquid formulation is an oxidizer, is highly corrosive at pH 2-3.5, and requires special disposal requirements. Sodium hypochlorite is a strong oxidizing agent, corrosive, toxic, and is reactive with ammonia to produce chloramines, with acids to produce chlorine gas, with organic matter to produce toxic disinfectant by-products, and with surfactants and fragrances to produce chlorinated toxic, volatile organic compounds (VOC). Electrochemically activated solution (ECA) must be generated on site, has a short shelf life, is a strong oxidizing agent, and shows reduced efficacy with organic loads. Chlorine dioxide must be generated on site due to its limited shelf life and its explosiveness at concentrations of 15% or higher, is a strong oxidizing agent, and shows reduced efficacy with organic loads. Quaternary ammonium compounds are cationic surfactants with toxic effects by all routes of exposure, concentrated solutions are corrosive, they can be inactivated by anionic compounds, and they have corrosive effects on metals, such as brass and copper, and vinyl. Methylene bisthiocyanates are pH sensitive and rapidly hydrolyzes at pH>8. Isothiazolinones are potent skin sensitizers and bacterial mutagens and causative for dermatitis. Thiocarbamates are volatile, possible sensitizers, show neuropathology toxicity, and are not compatible with polyurethane, milk steel, aluminum, brass, copper, and other plastics. Bronopol (2-bromo-2 nitropropane-1,3-diol) has potential for nitrosamine and formaldehyde formation on decomposition (suspected carcinogens).
There is a long felt need for a biocide formulation which will not have the shortcomings mentioned above.
It is an object of this invention to provide a biocide formulation (composition) which can be used in oil and gas exploration and production to treat hydraulic fracturing fluid.
It is a further object of this invention to provide a biocide formulation which is effective for treating other water used in the oil field, such as drilling water, field water systems, flood water, injection water, holding pond water, disposal well water and water holding tanks.
It is a further object of this invention to provide a biocide formulation which can be used in the processing of ore and mineral slurries, in the wood and pulp industry, and in the polymer, films, porous and nonporous structures. The biocide formulation is used to kill and prevent the growth of microorganisms.
It is another object to provide a biocide formulation that is safe for personnel working with the biocide formulation; the materials/equipment in contact with it, and is environmentally friendly.
It is also an object to provide a biocide formulation which is noncorrosive to equipment used, is effective at high salt concentration of field water, and does not interfere with other chemistries used in the hydraulic fracturing fluids, such as oxygen scavengers, hydrogen sulfide, and iron.
It is a further object that the biocide formulation be provided in a concentrate form which can be safely transported to the point of use, such as the well site, where it would be added to the fluid needing protection from microorganisms. The term biocide formulation and biocide composition are used interchangeably herein.
The above objects are accomplished by an embodiment of a biocide formulation comprising:
(a) water;
(b) at least one biocide selected from the group consisting of (i) a halogen substituted xylenol compound, (ii) a phenolic compound, (iii) an antimicrobial natural or essential oil, (iv) an antimicrobial component from natural or essential oil, and (v) combinations of at least two of (i), (ii), (iii) and (iv);
(c) at least one surfactant, wherein said surfactant is selected from the group consisting of anionic surfactant, amphoteric surfactant, nonionic surfactant, and blends thereof;
(d) at least one solubilizing agent; and
(e) optionally, said biocide formulation may also comprise ingredients selected from the group consisting of pH adjusters, metal chelators, and viscosity modifiers.
In a preferred embodiment, the biocide in the biocide formulation is parachlorometaxylenol (CAS No. 88-04-0).
In another embodiment, the surfactant in the biocide formulation is selected from the group consisting of potassium ricinoleate, sodium dodecyl sulfate, sodium lauryl ether sulfate, D-glucopyranose oligomeric decyl octyl glycosides, and mixtures thereof.
In a further embodiment, the solubilizing agent in the biocide formulation is selected from the group consisting of alpha-terpineol, propylene glycol, deionized water, and mixtures thereof.
In a preferred embodiment, the biocide formulation is a concentrate which comprises from about 5 to about 15 weight percent of the active biocide, but lower and higher concentrations are possible.
In another embodiment, the concentrated biocide formulation is added to field water to yield an active biocide component of from about 5 or less to about 5000 parts per million (ppm) in the resulting mixture. Preferably, the concentration of the biocide component is from about 100 to about 500 ppm.
The first necessary ingredient of the biocide formulation of this invention is the biocide. In one embodiment the biocide is a halogen substituted xylenol, with the preferred biocide being parachlorometaxylenol (hereinafter referred to as PCMX). PCMX is also known as 4-chloro-3,5-dimethyl-hydroxy benzene, 4-cholor 3,5-dimethyl phenol, 4-chloro 3,5 xylenol, and 4-chloro meta xylenol. PCMX is a chlorine substituted xylenol with a molecular formula of C8H9Cl0 and has a molecular weight of 156.5 with a CAS No. 88-04-0. PCMX's mechanism of antimicrobial action is by the denaturation of proteins and inactivation of enzymes in the microorganisms. Also likely, this agent, as for other phenolic compounds, alters the permeability of the cell membrane that could result in the uncoupling of oxidative phosphorylation, inhibition of active transport, and loss of pool metabdites due to cytoplasmic membrane damage. Compared to phenols, xylenols exhibit increased microbiocidal activity, on the order of from 30 to 60 times more. The chlorine substitution intensifies the microbiocidal potency.
Other biocides which may be used include phenols and substituted phenols, triclosan, trichlocarban, other phenolics such as para tertiary amylphenol (PTAP), o-benzyl-p-chlorophenol (BCP), and ortho-phenyl-phenol (OPP). Other biocides include benzalkonium chloride, benzethonium chloride, biguanide, and chlorohexidine gluconate.
As mention above, the halogen substituted xylenol (PCMX) is the preferred biocide, because it is very effective and environmentally friendly. However, one or more biocide may be used in combination with another biocide.
In another embodiment, the biocide is an antimicrobial natural or essential oil, which can be a natural or synthetic version, or components from such oils that are known to be antimicrobial. Natural or essential oils include terpineol, thyme, wild thyme, red thyme, thyme white, thymol, origanum, oregano and a main constituent carvacrol, lemongrass, lemon, orange, lime, lavender and its constituents lavandin and lavandula, tea tree and its constituents including terpinen-4-ol, wintergreen, eucalyptus and its components as 1,8-cineol and eucalyptol, menthol, cornmint, laurel, ziziphora, bay, sweet orange, cinnamon, cinnamon bark, rose, rosewood, clove, peppermint, rose geranium, geranium, meadowsweet, anise, orris, mustard, rosemary, cumin, neroli, birch, Melissa balm, ylang ylang, juniper, sweet fennel, garlic, cajeput, sassafras, heliotrope, pine, pine oils, parsley, violet, coriander, citron, citronella, patchouli, bergamot, sandalwood, eugenol, verbenone, geraniol, limonene, fennel, sesame, geraniol, hinokithiol, citral, terpinene, citronellal, citronellol, linalool, anethole, inenthone, carvone, camphor, and mixtures and components from such.
In another preferred embodiment, the biocide is a combination of PCMX and essential oil or components thereof.
The biocide formulation also contains as a necessary ingredient at least one surfactant. In one embodiment the surfactant is selected from the group consisting of anionic surfactant, amphoteric surfactant, nonionic surfactant, and blends thereof. Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate, sodium laureth sulfate of various levels of ethoxylation, TEA lauryl or laureth sulfate, MEA lauryl or laureth sulfate, potassium lauryl or laureth sulfate, sodium dodecyl sulfate, sodium octyl/decyl sulfate, sodium 2-ethyl-hexyl sulfate, sodium octyl sulfate, alkyl ethoxylates, alkyl ethoxylate sulfates, alkyl aryl sulfates, alkyl aryl sulfonates, sodium C14-C17 alkyl sec. sulfonate (paraffin sulfonate or sodium petroleum sulfonate), fatty acid soaps, natural acids saponified such as ricinoleate, alkylsulfonic acid salts, fatty alcohol sulfates, sodium xylene sulphonate, ammonium xylene sulphonate, sodium toluene sulphonate, sodium cumeme sulfate and other hydrotropes, alkyl phosphates as lauryl phosphate, sulfosuccinates as disodium lauryl and laureth sulfosuccinates, alphaolefin sulphonate, and alkyl phenol ether sulfate. Anionic surfactants such as derived from natural sources or recognized as GRAS (Generally Recognized As Safe) that are environmentally friendly are preferred.
Suitable amphoteric surfactants includes the general class of alkyl betaines as laurylamidopropyl betaine, oleyl betaine, ether amine oxides as lauryl dimethyl amine oxide, alkyl oxy propylamine dipropionate (amphoteric 12 as supplied by Air Products), cocoamidopropyl dimethyl amine oxide, phospholipids composed of diester and triester phosphatides, and naturally derived surfactants such as lecithins. Amphoteric surfactants such as derived from natural sources or recognized as GRAS that are environmentally friendly are preferred.
Suitable nonionic surfactants includes various linear or non-phenol alcohols or fatty acids, ethers of fatty alcohols, octylphenoxy polyethoxyethanol 2-dodecoxyethanol, ethoxylated alcohols, ethoxylated amines, ether amines and ether diamines as cocoamid DEA, cocoamide MEA, ethoxylated amines, esters as ethylene glycol monostearate, ethylene glycol distearate as polyoxyethylene sorbitan esters, polysorbates, linear ethylene oxide/propylene oxide and/or butylenes oxide block copolymers, poly(5) oxyethylene isodecyloxypropylamine, poly (5) oxyethylene isotridecyloxypropylamine, glycols such as propylene glycol, amine oxides as long chain alkyls, polyoxypropylene—polyoxyethylene block copolymers as methyl-oxirane polymer with oxirane, ethoxylated castor oil (castor oil polyoxyethylene ether), coco ethoxylated fatty acids (PEG-12 cocoate) and ethoxylated monoethanolamide of fatty acids of coconut oil (PEG-11 cocamide). Preferred nonionic surfactants include polysorbates as Tween 20, 40, or 80, Igepal, Tritons, and glucosides as decyl glucoside, lauryl glucosides, octyl glucosides, D-glucopyranoside C10 to C16 alkyl oligomer, D-glucopyranoside C6 to C12 alkyl oligomer, and ethyloxated amines and alcohols. These preferred nonionic surfactants readily biodegrade, are environmentally friendly and are gentle.
The biocide formulation of this invention also contains as a necessary ingredient at least one solubilizing agent. The solubilizing agent is necessary because many biocides, such as PCMX, are not soluble or very slightly soluble in water. The combination of the surfactant and solubilizing agent allows a stable emulsion to be made.
Suitable solubilizing agents include low molecular weight alcohols such as ethanol, propanol, isopropanol, glycols such as propylene glycol and polypropylene glycols. Ethanol, isopropyl alcohol, and propylene glycol are among the preferred solubilizing agents. Other preferred solubilizing agents include the cyclic terpenes such as pine oils and their components as the monoterpene alcohols, terpineols, or pine oil derivatives and their isomers alpha, beta and gamma, and aldehydes and ketones therefrom, limonenes including d-limonene, dipentenes, terpene hydrocarbons and terpene processing by-products and hydrocarbons including terpenes and terpenoids, turpentine—oil, myrcene fraction, hydroxyl, acetates, and 2,6-octadien-1-01,3,7-dimethyl-(2Z), and alcohols C10-terpenoidal, and benzene 1-methoxy-4-(1E)-1-propen-1-yl-.
Another necessary ingredient of the biocide formulation is water. Any normal source of water can be used as long as the water is reasonably clean and does not contain an excess of dissolved salts. In making the concentrated biocide formulation suitable for later use, deionized water is highly recommended to provide consistent quality.
The biocide formulation may optionally contain other ingredients, such as but not limited to pH adjusters, metal chelators, and viscosity modifiers.
Formulation pH adjusters include mineral acids and bases and organic acids and amines A preferred pH adjuster is hydrochloric acid and citric acid, and a preferred pH range is 6 to 9, and more preferred is 7.5 to 8.5. Metal chelators include various chemical agents to chelate or sequester metal ions in water. Some examples of chelators include organic acids, such as citric acid, sodium and potassium salts of ethylene diaminetetraacetic acid and nitrilotriacetic acid, sodium and potassium salts of methyl glycine diacetic acid, and bisphosphonates. To affect a decrease in the viscosity of the usable fluid solution, friction reducers can be employed. Friction reducers may include anionic, cationic, or amphoteric polyacrylamindes.
The preferred biocide formulation is made in a concentrated form as an emulsion using PCMX as the biocide or a mixture of PCMX and antimicrobial essential oils and/or components of such oils and mixtures thereof. The preferred biocide formulation is one utilizing a high flash point solubilizing agent, such as a glycol that reduces significantly the flammability of the formulation. By making the biocide in a highly concentrated form, advantages are achieved by limiting the volume needed to ship and a reduced shipping cost. The preferred concentrations of the biocide formulation are sufficiently low to be safe in their diluted and use form, environmentally friendly and sustainable, and safe to handle, to the user, and to equipment and/or materials that it needs to come in contact with, yet effective for bacterial control or kill. It is preferred that the surfactants be derived from natural and sustainable products, such as castor oil based anionic surfactant such as the potassium salt of ricinoleic acid with or without a cosurfactant such as sodium dodecyl sulfate or nonionic surfactants of various structures.
The preferred biocide formulation in concentrated form will have from (a) about 1 to about 20 weight percent biocide, preferably from about 5 to about 15 weight percent, and more preferably from about 8 to about 12 weight percent. The preferred biocide formulation in concentrated form will also have from (b) about 2 to about 50 weight percent surfactant, preferably from about 10 to about 40 weight percent. The preferred biocide formulation in concentrated form will also have from (c) about 20 to about 50 weight percent solubilizing agent. The remainder of the formulation is preferably deionized water.
The concentrated biocide formulation is added to water needing a biocide, such as hydraulic fracturing fluid or a mineral processing slurry in a concentration to give a level of the biocide from about 5 to about 5000 ppm, preferably from about 100 to about 500 ppm. Of course, the level used will depend on the fluid treated and the level of microorganisms in the fluid originally or after being used for its intended purpose. The level used can be adjusted higher or lower depending on the requirement in the particular field use.
Three specific highly preferred biocide formulations in concentrated form are as follows:
The main differences in the above three highly preferred biocide formulations is in the surfactant system used and in Formulation 3 the use of a single solubilizing agent. All formulations have a pH of from 8.0 to 8.6. Formulations 2 and 3 have proven to be better at high salt concentrations of the field water to be treated. Both formulations are highly effective for killing microorganisms.
Although the biocide formulations of this invention can be used in many applications, their primary focus is in treating oil field waters, particularly hydraulic fracturing fluids used in oil and gas production. The term “field water” as used herein means water obtained from any source but usually obtained from pond, river, stream, lake, water well, recycled water from a previous hydraulic fracturing job, treated water, and mixtures thereof. A single well normally uses 3 to 5 million gallons of water in a hydraulic fracturing procedure. Typically 10% to 15% of this water used will return to the surface as waste water. The waste water normally has high concentrations of salt and metals and therefore must be treated before disposal or re-use.
The three biocide formulations shown above are designed to be gentle and safe for the environment, the equipment coming in contact with it, and any personnel working with it. All formulations have an extended shelf life. They are effective when used under aerobic and anaerobic conditions, are active over a wide pH range, and are non-oxidizing, non-reactive with other chemistries used with it or in association with below ground applications and can be supplied as a concentrate to minimize shipping and transportation costs.
The biocide formulations of this invention are low toxicity (Category IV for oral, inhalation and dermal exposure) and thus safe for personnel use, no special handling requirements, and non-carcinogenic. The formulations also have a high flash point (greater than 200° F.) and thus are not an explosion hazard. Formulations 2 and 3 shown above are stable at varying concentrations of salt (mono and divalent) up to 12.5 Wt. % and are stable at up to 500 ppm biocide concentration in high salt (12.5 Wt. %) solutions. Tested formulation of the type 2 and 3 when tested are also stable at temperatures up to at least 189° F. (87° C.) tested.
The following examples 1-78 are shown to give specific formulations of biocide formulations which are concentrates designed to be further diluted within this invention. All % and ppm (parts weight per million) of the formulations are expressed as weight % or weight ppm unless otherwise indicated.
A composition having 6% potassium ricinoleate (surfactant), 10% isopropyl alcohol (solubilizing agent), 10% terpineol (solubilizing agent), 5% PCMX (biocide), with the remainder deionized water was made. The pH was adjusted with concentrated hydrochloric acid to pH 8.5.
Microbiological studies were carried out with the formulation of Example 1 and compared to tests with other known biocides. The field water used for testing came from a well in Texas. The biocides were tested at varying concentrations of the active biocide in the field water at active biocide concentrations from 94 parts per million (ppm) to 500 ppm. The biocide of Example 1 was tested along with several known biocides. The known biocides included 2,5-dimethyl-1,3,5-thiadiazinane-2-Thione (Dazomet), tetrakis hydroxylmethyl phosphonium sulfate (THPS), glutaraldehyde, and dibromocyanoacetamide (DBNPA). In general, the kill of sulfate reducing bacteria (SRB) and acid producing bacteria (APB) varied as a function of the concentration for the individual biocides. At 94.2 ppm of PCMX, there was complete kill of SRB and APB. There was not complete kill when using Dazomet at 270 ppm. There was complete kill at 150 ppm THPS, and complete kill at 250 ppm glutaraldehyde, and complete kill with 20 ppm DBNPA. This Example shows the effectiveness of the biocide formulation of this Example 1 to kill SRB and APB at a concentration of 94 ppm active PCMX.
A composition with 12% potassium ricinoleate, 20% isopropyl alcohol, 20% terpineol, 10% PCMX, with the remainder deionized water was made. The pH was adjusted with concentrated hydrochloric acid to pH 8.5.
A composition with 12% castor oil salts, 20% isopropyl alcohol, 20% pine oil 150, 10% PCMX, with the remainder deionized water was made. The pH was adjusted with concentrated hydrochloric acid to pH 8.51.
A composition with 12% potassium ricinoleate, 20% isopropyl alcohol, 20% terpineol, 10% PCMX, with the remainder deionized water was made. The pH was adjusted with concentrated hydrochloric acid to pH 8.51.
A composition with 6% potassium ricinoleate, 1.5% sodium dodecyl sulfate, 8.75% isopropyl alcohol, 1.25% phenoxetol, 5.45% terpineol, 5% PCMX, 1% polyphosphate, with the remainder deionized water was made. The pH was not adjusted and was 8.33.
Microbiological kill studies were carried out in field waters considered to be problematic. Concentrations of up to 150 ppm PCMX final concentration were evaluated per the standard “Determining Loading Volumes for Sample Water and Biocides.” PCMX concentrations of >100 ppm showed complete control of APB, SRB, and slime producing bacteria (SPB). There was no discrimination in kill among the different bacterial species.
A composition with 6% potassium ricinoleate, 1.5% sodium dodecyl sulfate, 8.75% isopropyl alcohol, 1.25% phenoxetol, 5.18% terpineol, 0.27% lemongrass, 5% PCMX, 1% polyphosphate, with the remainder deionized water was made. The pH was not adjusted and was 8.37.
A composition with 12% potassium ricinoleate, 3% sodium dodecyl sulfate, 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water was made. With various individual batches made, the pH was adjusted with concentrated hydrochloric acid to 8.52 to 8.56.
Microbicidal studies were carried out with the formulation of this Example 7. A field water sample was used to dilute the formulation and growth media was added. The testing was per the standard “Determining Loading Volumes for Biocides.” The samples to be tested were placed in bottles and observed for growth of bacteria. Control samples (no biocide) showed that for sulfate reducing bacteria (SRB), 5 bottles turned (showed growth) at five days and for acid producing bacteria (APB) at one day. For the SRB concentrations up to 150 ppm PCMX were studied. Significant reductions in SRB were seen at concentrations ≧100 ppm and shown to be directly related to the PCMX concentration. For the APB samples, concentrations of up to 100 ppm PCMX were studied. A significant reduction in APB was seen at 100 ppm PCMX. The diluted sample was also tested after the sample had experienced four freeze/thaw cycles and the sample with growth media added was tested with PCMX concentrations up to 100 ppm PCMX. A significant reduction in SRB and APB were seen at 100 ppm PCMX concentration. The repeated freezing process did not have any significant effect on the microbicidal properties of the formulation.
A comparable laboratory study was conducted using two field waters with high hydrogen sulfide concentrations of 42 and 24 ppm respectively. These waters were not supplemented with growth media and the controls showed significantly lower numbers of bottles that turned for the SRB and APB. For the 42 ppm hydrogen sulfide concentration water, testing was carried out with PCMX concentrations up to 100 ppm. At the concentration of 100 ppm PCMX, there was significantly better control of SRB and APB, with no more than one bottle showing growth after 10 days of study. For the 24 ppm hydrogen sulfide concentration water, testing was carried out with PCMX concentrations up to 125 ppm. At concentrations of 100 ppm and higher PCMX, there was significantly better kill and less bottles showing bacterial growth.
The formulation of this Example 7 was tested by an independent laboratory for microbiological testing at a concentration of 200 ppm PCMX in deionized water and in a 2.5 wt. % sodium chloride solution at room temperature (23±2° C.). The organisms studied were Bacillus cereus ATCC #35857, Pseudomonas Fluorescens ATCC #13525, and Aspergillus niger spores. The contact times for testing were 1 and 3 hours. For the vegetative bacteria Bacillus cerus and Pseudomonas fluorescens at all times and for both organisms the number of organisms remaining were <1 organism. The log reductions were greater than 6 logs demonstrating significant antibacterial activity. For the A. niger spores tested with 2.5 wt. % sodium chloride the reductions in bacteria reductions were 91.04% and 92.74% at 1 and 3 hours, respectively.
Toxicological studies were also carried out on this formulation of Example 7. In an acute dermal irritation testing in albino rabbits, the formulation was rated as slightly irritating and assigned to Toxicity Category IV per Proposed Rule, FR Vol. 49, No. 188. In an acute dermal toxicity and relative skin irritancy testing in albino rats, the formulation had an LD50 of greater than 5050 mg/kg body weight in males and females and there were no signs of dermal irritation at any observation during the study period. In an skin sensitization study in guinea pigs (Buehler method) the formulation did not elicit a sensitizing reaction. In acute eye irritation testing in albino rabbits (three), the formulation had a maximum average irritation score of 36.7 and was severely irritating and was assigned to Toxicity Category I. In an acute oral toxicity testing in rats, the acute oral LD50 was greater than 5000 mg/kg and was assigned to Toxicity Category IV. In an acute inhalation toxicity in rats, the LC50 was greater than 2.26 mg/L in males and females and was assigned to Toxicity Category IV.
These tests indicate that the formulation of Example 7 is not only effective as a biocide, but also is relatively safe and non-toxic.
A composition with 12% potassium ricinoleate, 2.8% ricinoleamidopropyl PG-dimonium chloride phosphate, 20% isopropyl alcohol, 10.9% terpineol, 10% PCMX, with the remainder deionized water was made. Without pH adjustment the pH was about 8.5 to 9.
A composition with about 10% mixture of an amine oxide and D-glucopyranoside, 10% disodium capryloampho dipropionate, 20% isopropyl alcohol, 10.9% terpineol, 10% PCMX, and the remainder deionized water was made. Without pH adjustment the pH was about 8.5.
A composition with about 32% of an ethoxylated amine, about 16% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13 rich,C11-14-isoalkyl)oxy)propyl) derivatives, about 1.7% b-alanine, N-(2-Carboxyethyl)-N(3-(decyloxy)propyl)-, monosodium salt, 20% isopropyl alcohol, 10.9% terpineol, 10% PCMX, with the remainder deionized water was made. Without pH adjustment the pH was 8.5-9.
In this example, compositions were made with essential oils. As pre-mixes, for example, solutions of the essential oils as an oil mix (thyme, wintergreen, eucalyptus, and menthol), carvacrol, lemongrass, origanum, and thyme white were combined with terpineol and propylene glycol. The solutions were crystal clear with the exception of the thyme white mix which was slightly whitish. The solutions carried the characteristic fragrance of the essential oil used. These solutions could then be combined with the surfactant package of choice to produce a biocide concentrate and further diluted with water to produce solutions of the desired concentration. As an example, a concentrate composition was produced of about 10% of the oil mix, about 10.9% terpineol, about 20% propylene glycol, about 12% potassium ricinoleate, about 3% sodium dodecyl sulfate, with the remainder water. The pH of this solution was about 9-9.5 and the solution was clear. The addition of water is not necessary if a higher essential oil concentration is desired. This concentrate is dilutable with water to the desired essential oil concentration. For a composition containing the oil mix a use dilution was made of about 1000 ppm of the oil mix and the particle size measured. The particle size was about 54 nm with a zeta potential of about 60 mV and a conductivity of 0.4 mS/cm.
A concentrate composition was produced of about 10% of the carvacrol oil, about 10.9% terpineol, about 20% propylene glycol, about 12% potassium ricinoleate, about 3% sodium dodecyl sulfate, and the remainder water. The pH of this solution was about 9-9.5 and the solution was amber clear. The addition of water is not necessary if a higher essential oil solution concentration is desired. This concentrate is dilutable with water to the desired essential oil concentration.
A composition web site produced with about 32% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 16% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14-isoalkyl)oxy)propyl)-, monosodium salt, 20% propylene glycol, 10.9% terpineol, 10% PCMX, and the remainder deionized water. Without pH adjustment the pH was 8.5.
A composition was made with about 8.8% deoiled lecithin (as from ADM of trade name Ultralec), 10% PCMX, 10.9% terpineol, 20% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 6.
A 0.2% PCMX solution was made by dilution of the composition in deionized water. Without pH adjustment the pH was about 5-5.5.
A composition was made with about 24% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 12% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N(3-(C13-rich,C11-14-isoalkyl)oxy)propyl) derivatives, about 1.3% b-alanine, N-(2-carboxyethyl)-N(3-(decyloxy)propyl)-, monosodium salt, 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 9. An about a 0.2% PCMX concentration of this composition was made by dilution with water and had a pH of about 8.5.
A composition was made with about 24% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 12% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14 isoalkyl)oxy)propyl) derivatives, about 1.3% b-alanine, N-(2-carboxyethyl)-N(3-(decyloxy)propyl)-, monosodium salt, about 6% C9-C11 ethoxylated alcohols (with EO/alcohol ratio of 5.5-6.5), 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 9. An about a 0.2% PCMX concentration of this composition was made by dilution with water and had a pH of about 8.5.
A composition was made with about 24% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 12% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14-isoalkyl)oxy)propyl) derivatives, about 1.3% b-alanine, N-(2-carboxyethyl)-N(3-decyloxy)propyl)-monosodium salt, about 6% methyl-oxirane polymer with oxirane, 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 8.5. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 8.5.
A composition was made with about 23% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 11.5% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14 isoalkyl)oxy) propyl) derivatives, about 1.2% b-alanine, N-(2-carboxyethyl)-N (3-(decyloxy)propyl)-, monosodium salt, about 5% C9-C11 ethoxylated alcohols (with EO/alcohol ratio of 5.5-6.5), 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 9. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 8.5.
A composition was made like Example 7, but with the addition of about 0.75% of the bisphosphonate, tetrasodium 1-hydroxyethylidene-1,1-diphosphonate. Without pH adjustment the pH was about 10.5.
A composition was made with about 24% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 12% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14-isoalkyl)oxy)propyl) derivatives, about 1.3% b-alanine, N-(2-carboxyethyl)-N(3-(decyloxy)propyl)-, monosodium salt, about 6% C9-C11 ethoxylated alcohols (with EO/alcohol ratio of 5.5-6.5), 14.9% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 9. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 8.5.
A composition was made with about 40% 2-dodecoxyethanol, 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5.5 An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 5.
A composition was made with about 40% 2-dodecoxyethanol, 20% propylene glycol, 10.9% d-limonene, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5.5. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 5.
A composition was made with about 24% of an ethoxylated amine (poly (5) oxyethylene isodecyloxypropylamine), about 12% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14-isoalkyl)oxy)propyl) derivatives, about 1.3% b-alanine, N-(2-carboxyethyl)-N(3-(decyloxy)propyl)-, monosodium salt, about 6% methyl-oxirane polymer with oxirane, 14.9% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 9. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 8.5.
A composition was made with about 30% 2-dodecoxyethanol, 6% methyl-oxirane polymer with oxirane, 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5-5.5.
A composition was made with about 35% 2-dodecoxyethanol, 5% methyl-oxirane polymer with oxirane, 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5-5.5.
A composition was made with about 23% of an ethoxylated amine (poly(5) oxyethylene isodecyloxypropylamine), about 11.5% of polyoxy-1,2-ethanediyl,a,a-(iminodi-2,1-ethanediyl)bis(w-hydroxy-,N-(3-(C13-rich,C11-14-isoalkyl)oxy)propyl) derivatives, about 1.2% b-alanine, N-(2-carboxyethyl)-N(3-(decyloxy)propyl)-, monosodium salt, about 5% C9-C11 ethoxylated alcohols (with EO/alcohol ratio of 7.9-8.9), 20% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 9.5. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 8-8.5.
A composition was made with about 40% 2-dodecoxyethanol, 15% propylene glycol, 10.9% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5.5.
A composition was made with about 40% 2-dodecoxyethanol, 20% propylene glycol, 5.45% d-limonene, 5.45% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5.5. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 5.
A composition was made with about 35% 2-dodecoxyethanol, 5% methyl-oxirane polymer with oxirane, 20% propylene glycol, 5.45% d-limonene, 5.45% terpineol, 10% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5.5. An about a 0.2% PCMX concentration was made by dilution with water and had a pH of about 5.
A composition was made with about 35% 2-dodecoxyethanol, 5% of a mixture of castor oil polyethylene ether with PEG-12 cocoate and PEG-11 cocamide, 20% propylene glycol, 5.45% d-limonene, 5.45% terpineol, 10.1% PCMX, with the remainder deionized water. Without pH adjustment the pH was about 5.5.
A composition was made with about 27-35% sodium laureth sulfate (CAS No. 68585-34-2), 8-13% lauryl glucoside (D-glucopyranoside, C6-12-alkyl, oligomer)(CAS No. 113976-90-2), 8-13% ethanol (CAS No. 64-17-5), 2-5% sodium chloride, 17% PCMX (CAS No. 88-04-0), with the remainder deionized water. Without pH adjustment the pH was about 6-6.5.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 8.5-9.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water.
A composition was made with about 30% sodium laureth sulfate, 10% lauryl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 9-9.5.
A composition was made with about 28.5% sodium laureth sulfate, 9.5% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 9.5-10.
A composition was made with about 27% sodium laureth sulfate, 9% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 10.
A composition was made with about 24% sodium laureth sulfate, 8% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 10.
A composition was made with about 25% sodium laureth sulfate, 7% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 10.
A composition was made with about 24% sodium laureth sulfate, 8% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 10.
A composition with about 30% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 9.5-10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment the pH was about 5.5.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10-10.5.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10-10.5.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water.
A composition was made with about 25% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 20% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10.
A composition was made with about 25% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 20% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10.
A composition was made with about 29% sodium laureth sulfate, about 6.5% D-glucopyranose, about 6.5% cocamidopropyl betaine, about 2.9% sodium chloride, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 5.5.
A composition was made with about 20% sodium laureth sulfate, about 4.5% D-glucopyranose, about 4.5% cocamidopropyl betaine, about 2% sodium chloride, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deonized water. Without pH adjustment, the pH was about 5.5.
A composition was made with about 25% sodium laureth sulfate, about 5.5% D-glucopyranose, about 5.5% cocamidopropyl betaine, about 2.5% sodium chloride, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 5.5.
A composition was made with about 30% sodium laureth sulfate, 8% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 9.
A composition was made with about 30% sodium laureth sulfate, 8% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 9.
A composition was made with about 28% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10.
A composition was made with about 28% sodium laureth sulfate, 12% decyl glucoside, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment, the pH was about 10.
A composition was made with about 28% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 18.9% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment, the pH was about 10.
A composition was made with about 28% sodium laureth sulfate, 11% decyl glucoside, 0.66% alkyloxy propylamine dipropionate, 10% PCMX, 10.9% terpineol, 15% propylene glycol, with the remainder deionized water. Without pH adjustment, the pH was about 10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10% PCMX, 10.9% terpineol, 16% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment, the pH was about 10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10.25% PCMX, 10.9% terpineol, 15.7% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment, the pH was about 10.
A composition was made with about 30.4% sodium laureth sulfate, 10% glycoside, 10.25% PCMX, 10.9% terpineol, 15.7% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment, the pH was about 10.
A composition was made with about 30.43% sodium laureth sulfate, 10% glucoside, 10.25% PCMX, 10.9% terpineol, 15.7% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment the pH was about 10. With pH adjusted with concentrated HCl, the pH was 8.59.
A composition was made with about 30% sodium laureth sulfate, 10% glucoside, 10.25% PCMX, 10.9% terpineol, 15.7% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment the pH was about 10. With pH adjusted with concentrated HCl, the pH was 8.55.
In an independent laboratory, microbiological testing was conducted with the formulation of Example 63 at about 200 ppm PCMX in deionized and in a 2.5% sodium chloride solutions at room temperature (23±2 C). The organisms studied were Bacillus cereus ATCC#14579, Pseudomonas fluorescens ATCC#13525, and Aspergillus niger spores ATCC#9642. The contact times for testing were less than one minute, 1 and 3 hours. For the vegetative bacteria Bacillus cerus and Pseudomonas fluorescens at all times and for both organisms the number of organisms remaining were <1 organism (no growth). The log reductions were greater than 4 logs demonstrating significant antibacterial activity. For the A. niger spores tested with 2.5% sodium chloride solution the reductions were 58.75% and 77.78% at 3 hours respectively.
On formulation of Example 63 independent microbiological testing was conducted at about 200 ppm PCMX in 2.5% sodium chloride solutions at room temperature (20 C) per ASTM E2315-03 at 1 hour contact time. The organism studied was Desulphovibrio desulfuricans ATCC#29577. At an initial concentration of 2.0×107 cfu/ml the reduction at 1 hour was 92.5% (1.50×106) or a reduction of 18,500,000 organisms per ml.
A composition was made with about 26.2% sodium C14-C17 alkyl sec. sulfonate, 10% glucoside, 10.25% PCMX, 10.9% terpineol, 15.7% propylene glycol, with no added deionized water, as some of the ingredients contained water. Without pH adjustment, the pH was about 10.
A composition was made with about 30% sodium laureth sulfate, 10% decyl glucoside, 10.25% PCMX, 10.9% pine oil (Unipine 85), 15.7% propylene glycol with no added deionized water as some of the ingredients contained water. Without pH adjustment the pH was about 10.
A composition was made with 12% potassium ricinoleate, 3% sodium dodecyl sulfate, 20% propylene glycol, 10.9% pine oil (Unipine 85), and 10.2% PCMX with the remainder deionized water. Without pH adjustment the pH was 9-9.5.
A composition with about 28.8% sodium laureth sulfate, 9.6% decyl glucoside, 11% PCMX, 11.64% pine oil (Unipine 85), 16.75% propylene glycol with no added deionized water, as some of the ingredients contained water. Without pH adjustment the pH was about 9.5.
A composition was made with about 30.0% sodium laureth sulfate, 10.0% decyl glucoside, 10.25% PCMX, 10.9% pine oil (Unitene LE), 15.7% propylene glycol with no added deionized water, as some of the ingredients contained water. This solution formed a gel.
A composition was made with about 28.0% sodium laureth sulfate, 9.3% decyl glucoside, 10.2% PCMX, 10.9% pine oil (Unitene LE), 20.0% propylene glycol with no added deionized water, as some of the ingredients contained water.
A composition was made with about 25.2% sodium laureth sulfate, 8.4% decyl glucoside, 10.2% PCMX, 10.9% pine oil (Unitene LE), 20.0% propylene glycol with 5.9% added deionized water.
A composition was made with about 26.6% sodium laureth sulfate, 8.9% decyl glucoside, 10.2% PCMX, 10.9% pine oil (Unitene LF), 22.95% propylene glycol with no added deionized water, as some of the ingredients contained water. Without pH adjustment the pH was about 9.
A composition was made with about 30.0% potassium ricinoleate, 3.0% sodium dodecyl sulfate, 10.2 PCMX, 10.9% pine oil (Unitene LF), 20.0% propylene glycol with 15.81% added deionized water. Without pH adjustment the pH was about 9.5.
A composition was made with about 28.3% sodium laureth sulfate, 9.5% decyl glucoside, 10.24% PCMX, 30.0% propylene glycol with no added deionized water, as some of the ingredients contained water. Without pH adjustment the pH was about 8.5-9.
A composition was made with about 30.0% potassium ricinoleate, 3.0% sodium dodecyl sulfate, 10.25% PCMX, 30.0% propylene glycol with 16.63% added deionized water. Without pH adjustment the pH was about 8.5-9.
A composition was made with about 28.0% sodium laureth sulfate, 9.3% decyl glucoside, 10.2% PCMX, 10.9% d-limonene, 20.0% propylene glycol with no added deionized water, as some of the ingredients contained water. With no pH adjustment pH was about 8-8.5.
A composition was made with about 28.0% sodium laureth sulfate, 9.3% decyl glucoside, 10.2% PCMX, 10.9% Terpene Special (IFF, includes hydrocarbons, terpene processing by-products, terpene hydrocarbons, by products; alcohols, C10-terpenoidal; benzene, 1-methoxy-4-(1E)-1-propen-1-yl-; terpenes and terpenoids, turpentine-oil, myrcene fraction, hydroxyl, acetates), 20.0% propylene glycol with no added deionized water, as some of the ingredients contained water. With no pH adjustment pH was about 9.
A composition was made with about 28.0% sodium laureth sulfate, 9.3% decyl glucoside, 10.2% PCMX, 10.9% Unitene D (IFF, hydrocarbons, terpene processing by-products, terpene hydrocarbons, by product), 20.0% propylene glycol with no added deionized water, as some of the ingredients contained water. With no pH adjustment pH was about 9-10.
A composition was made with about 28.0% sodium laureth sulfate, 9.3% decyl glucoside, 10.2% PCMX, 5.9% Unitene D (IFF, hydrocarbons, terpene processing by-products, terpene hydrocarbons, by product), 25.0% propylene glycol with no added deionized water, as some of the ingredients contained water. With no pH adjustment pH was about 8.5-9.
The following Examples are presented to evaluate various biocide formulations produced in Examples 1-78 above in various waters, including several waters obtained from actual well drilling sites and manufactured waters with various salt levels. The manufactured waters were produced by weighing in specific chemistries and diluting with deionized water. Various volumes/weights of the water were placed in laboratory glassware and mixed gently with a magnetic stirrer at ambient temperature. A volume/weight of the specific formulations was added drop wise to the stirring water and observations of the solution conditions made. Specific attention was made to observe any oil-like separation, precipitate formed, and cloudiness or opaqueness in the solution. Observations were typically made over hours and days without the solution being continually mixed. Specific materials or methods related to individual tests are described in the Examples that follow.
Twelve different field water samples (A-L) were obtained from actual drilling well sites. The twelve different waters and their properties are shown in Table 1 below.
Overall means and range of the properties of the twelve field waters are shown in Table 2 below.
The field waters were evaluated with biocide formulations having PCMX as the biocide, propylene glycol as the solubilizing agent, and varying surfactants. PCMX concentrations at 100 ppm and 500 ppm were evaluated. The observations are shown in Table 3 below.
This Example is presented to evaluate select biocide formulations shown in Examples 1-78 above in deionized water with 6% potassium chloride and 0.5% calcium chloride added as well as in 2 field waters (J and L) at a biocide concentration of 500 ppm PCMX. From prior testing with varying salt compositions, the 6% potassium and 0.5% calcium chloride was recognized to be a “worst” case water in terms of demonstrating instability (precipitates forming or oil-like materials separating) of the biocide formulations. For emulsion formulations in general, salting studies have been demonstrated to provide comparative way of comparing formulations for stability. The deionized (DI) water used was produced in a laboratory Barnstead Nanopure Diamond/Diamond RO system. The DI water had a resistivity of about 18.2 Mohm-cm. The solution was prepared by weighing in the salts and water to two decimal places. The pH of the resulting solution was 5.5 as tested using pH-indicator strips. All reusable glassware was cleaned and dried before use. Solutions were volumetrically measured using a 25 ml sterile serological pipette (for the salt water) and a 1 ml sterile serological pipette for the biocide formulations. The salt water was added to a glass beaker and gently mixed with a magnetic stirrer. The biocide formulation was then added. In this study, 100 ml of the salt water was used along with 0.5 ml of the biocide formulation, thus giving a PCMX concentration of about 500 ppm, except in one sample where 340 ppm was used. All solutions had 6% potassium chloride and 0.5% calcium chloride unless otherwise noted. In some formulations the tests were repeated on different days to evaluate repeatability of the results.
Observations were made initially-1 and at various times. The observations for the various formulations and water used are shown below in Table 4.
The results show that the water type makes a difference. Significant differences were seen with DI water with no salt (shown as control in the Table 4 above) and when DI water with 6% potassium chloride and 0.5% calcium chloride was used. The high salt water is much more likely to cause instability of some of the solutions. When the appearance of oil is observed, with mixing the oil may re-absorb suggesting the need for mixing. Density differences may also account for this. The observations and the effects seen relate to the degree and amount of mixing. The formulations are emulsions and their integration into the varying water types relate to the degree and amount of mixing.
Separation of material (not oily) occurs in some cases and relates to the time between stiffing or mixing even though this stirring/mixing was considered very gentle and minimal. When surface material is present it mixes in well with very gentle stirring.
This Example is presented to evaluate select biocide formulations, at a concentration of 200 ppm PCMX, shown in Examples 1-78 above in deionized water with 6% potassium chloride and 0.5% calcium chloride. Testing at about 200 ppm PCMX was carried out, and it is the level expected to be required for most field waters. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1 and at various times. DI water was used in all solutions. The observations for the various formulations are shown below in Table 5. In some formulations the tests were repeated on different days to evaluate repeatability of the results.
The biocide formulations in Example 7 appears suitable for most waters tested. In adding the biocide formulations the more vigorous the mixing the better. Emulsion technology generally relies on good mixing of the water and emulsion product; this was shown to be particularly important for the biocide formulation of Example 13. For the high salt concentration waters the anionic biocide formulations (Examples 13, 16 and 18) produced less precipitate. Also, a water treatment chemical precipitates materials that are precipitated by the anionic surfactant containing biocide formulations. Clarity of the solution is very likely related to the particle size of the emulsion and this is likely related to the salt concentration and pH.
Comparatively the biocide formulation of Example 27 looked better than Example 25. Comparative testing of biocide formulations of Examples 25, 27, 28 and 29, showed 27 and 29 to be better. Formulation 73 performed very well.
This Example is presented to evaluate select biocide formulations from Examples 1-78 at a concentration of 100 ppm PCMX. Deionized water with 6% potassium chloride and 0.5% calcium chloride (salt water) was studied as well as deionized water with 2% sodium chloride added, along with a control with plain deionized water. The deionized water and salt solutions were made as described in Example 80 above.
Observations were made initially-1, after last solution prepared-2, 3 hours after start of study-3, about 24 hours after start-4, about 33 hours after start-5, about 48 hours after start-6, and about 120 hours after start-7 or as otherwise noted. The observations are shown below in Table 6.
The results suggest that the water type makes a difference. Biocide formulation from Example 7 was evaluated in 3 different waters (DI water, 6% potassium chloride and 0.5% calcium chloride, and 2% sodium chloride).
Separation of material (not oily) occurs in some cases and relates to the time between stiffing or mixing even though this stiffing or mixing was very gentle and minimal. When surface material is present it mixes in well with gentle stirring.
This Example is presented to evaluate the biocide formulation of Examples 7 and 63, at a concentration of 500 ppm PCMX, in deionized water with 2% sodium chloride and 0.05% calcium chloride added to the deionized water. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, and after noted times. The observations for the formulations are shown below in Table 7.
This Example is presented to evaluate various biocide formulations, at a concentration of 200 ppm PCMX, shown in Examples 1-78 above in deionized water with 2% sodium chloride and 0.05% calcium chloride. One “control” solution was tested with no salt. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, after about 5 hours-2 from start, after about 24 hours-3 after start, and about 45 hours-4 after start of study, and after other noted time. The observations for the various formulations are shown below in Table 8.
The results indicate that the presence of calcium chloride causes changes not seen without it. In particular, for the biocide formulation of Example 7 a precipitate is formed initially when calcium chloride is present. The amount of precipitate is related to the level of calcium chloride present. No precipitate is observed when calcium chloride is not present.
There are fewer changes compared to testing with higher salt levels (6% potassium chloride and 0.5% calcium chloride. With less salt present, no oil separation was ever noted. Some sedimented or surface material was noted in some cases, but this material mixed in well when the solution was gently stirred. This suggests that with those formulations a periodic mixing of the solution would be useful to keep it suspended.
This Example is presented to evaluate various biocide formulations, at a concentration of 100 ppm PCMX, shown in Examples 1-78 above in deionized water with 2% sodium chloride and 0.05% calcium chloride added. One “control” solution was tested with no salt. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, after about 5 hours-2, after about 24 hours-3, after about 45 hours-4, after the start of the study, and at other noted times. The observations for the various formulations are shown below in Table 9.
As noted for testing at 100 ppm PCMX, the results indicate that the presence of calcium chloride causes changes not seen without it. The amount of precipitate for the biocide formulation of Example 7 is related to the level of calcium chloride present and was less when the formulation concentration was reduced to 100 ppm from 200 ppm. In testing the biocide formulations of Examples 25 and 27 were less hazy than the formulations of Examples 28 and 29. Formulation 63 showed the least changes.
This Example is presented to evaluate the biocide formulations of Examples 7, 60, 63 and 73, at a concentration of 500 ppm PCMX, in deionized water with 2.5% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, and at various times as indicated. The observations are shown below in Table 10.
This Example is presented to evaluate the biocide formulations of Examples 7, 27, 63 and 73 at a concentration of 200 ppm PCMX in deionized water with 2.5% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, and after various times as indicated. The observations are shown below in Table 11.
This Example is presented to evaluate the biocide formulations of Examples 7, 3 and 73 at a concentration of 100 ppm PCMX in deionized water with 2.5% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, and at various times indicated. The observations are shown below in Table 12.
This Example is presented to evaluate various biocide formulations from Examples 1-78 at a concentration of 100 ppm PCMX in deionized water with 2% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, after about 3.5 hours-2, after about 67 hours-3. The observations are shown below in Table 13.
The results indicate that there are fewer changes compared to testing with 6% potassium chloride and 0.5% calcium chloride water and that with less salt no oil separation was noted. Some sedimented or surface material was noted in some cases but this material mixed in well when the solution was gently stirred. This suggests that with those formulations a periodic mixing of the solution would be useful to keep it suspended.
This Example is presented to evaluate various biocide formulations from Examples 1-78 at a concentration of 500 ppm PCMX in deionized water with 2.5% calcium chloride, 2.5% potassium chloride, and 7.5% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Formulation 32 was evaluated for the effects of high temperature, before and after adding biocide. Formulation 45 was also evaluated at high temperature. Observations were made initially-1, and at various indicated times. The observations are shown below in Table 14. In some formulations the tests were repeated on different days to evaluate repeatability of the results.
Evaluations were made with formulation of Example 32 both heating the saline solution to about 185° F. (85° C.) after adding the formulation to DI water and before adding the biocide formulation to the DI water. Formulation of Example 45 was also evaluated by heating (to 85° C.) the mixture of DI water and biocide formulation. With the exception of volume reduction and the solutions being more translucent after heating, no other changes were noted.
Observations were also undertaken to assess the dissolution of PCMX in the high saline solutions. The solubility of PCMX in water is 300 ppm, per its MSDS. When the temperature was raised to 85° C., there remained undissolved PCMX in crystalline form. When the temperature was lowered, a sediment appeared and undissolved material appeared in solution. It is likely that some PCMX dissolved and then recrystallized, falling out of solution at the lower temperature (less than 35° C.).
Additional evaluations were made on a DI water solution with the formulation of Example 73 at about 500 ppm PCMX. Initially the solution was crystal clear. Heating to 190 F(88 C) and then cooling it was noted that there were no changes, there was no ppt. nor separation noted. Evaluations were also made on 73 in “API” brine with 2.5% CaCl2+2.5% KCI+7.5% NaCl in DI water. The solution was initially opaque. After heating to 194 F(90 C) the only noted change was that the solution was less opaque.
Biocide formulations of Examples 32, 33, 43, 46, 48 and 49 showed no surface oil, and looked opaque suggesting these as good biocide formulations for use with high concentration brine solutions.
This Example is presented to evaluate various biocide formulations from Examples 1-78 at a concentration of 200 ppm PCMX in deionized water with 2.5% calcium chloride, 2.5% potassium chloride, and 7.5% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, and at various indicated times. The observations are shown below in Table 15.
An evaluation was also undertaken to assess the dissolution of PCMX in the high brine solution. The solubility of PCMX in water is 300 ppm per its MSDS, at 200 ppm PCMX (pH 5) the temperature was raised to 85° C. Up to this temperature there remained undissolved PCMX in crystalline form. While reducing the temperature to about 22° C., no sediment appeared. It is possible that some PCMX dissolved but not to the level of 200 ppm and there was no recrystallization on cooling.
This Example is presented to evaluate various biocide formulations from Examples 1-78 at a concentration of 100 ppm PCMX in deionized water with 2.5% calcium chloride, 2.5% potassium chloride, and 7.5% sodium chloride added. The DI water and salt solutions were made as in Example 80 above. Observations were made initially-1, and at various indicated times. The observations are shown below in Table 16.
This Example is presented to evaluate various biocide formulations from Examples 1-78 at a concentration of 500 ppm PCMX in deionized water (no salt). The composition of Example 73 was also evaluated at 2400 ppm of the biocide. The DI water was made as in Example 80 above. The water was added to a glass beaker and gently mixed with a magnetic stirrer. The biocide formulation was then added. Observations were made initially-1 and at various noted times. The observations are shown below in Table 17.
This Example is presented to evaluate Citrus Mulse (CM) as the 2-dodecoxyethanol component in various biocide formulations of Example 1-78 above, in making the biocide concentrate formulation. Also, some additional formulations were evaluated that were variations on the Examples 1-78 formulations. These additional formulations are indicated in the table below as “T” numbers (T12, T16, T18, T21, and T26-T31). The formulations were evaluated for their ability to make stable emulsions. The ingredients were mixed together and the status of the emulsion were observed. If the formulation formed a stable emulsion its status was listed as OK. If the emulsion was not stable the status was listed as Abort. The formulations and status are shown below in Table 18.
Discussion of the observations and results from this Example 94 follows below. For formulation T12 when the final concentration of methyl-oxirane polymer with oxirane was increased from 2.0% to 5.8%, the solution was still not clear. Per formulation of Example 24 (which was OK), additional methyl-oxirane polymer with oxirane may be needed in formulation T12. For formulation T21 when the level of propylene glycol was increased from 14.9% to 19.9%, the solution was clear and looked OK, but is then more comparable to the formulation of Example 29. For formulation T26 when the Citrus Mulse level was increased from 35% to 38.1%, the solution was clear, suggesting a formulation like in Example 27 could be made with as low as about 38% CM. For formulation T27 when the CM level was increased from 35% to 36.9%, the solution was clear and is approaching the formulation of Example 28 or Example 29 without the methyl-oxirane polymer with oxirane and suggests that the CM level may be as low as about 37% for the formulation of Example 28 or increased to about 37% without the methyl-oxirane polymer with oxirane. For the formulation T28, when the CM level was increased from 35% to 36.9%, the solution was clear and is approaching the formulation of Example 22. This suggests that the CM level of Example 22 may be reduced to as low as about 37%. For the formulation T29 when the level of CM was increased from 35% to 36.9%, the solution was clear and is approaching the formulation of Example 25 without the methyl-oxirane polymer with oxirane. This suggests that the level of CM may be as low as about 37% for the formulation of Example 25. For the formulation T30 when the level of CM was increased from 35% to 38.1%, the solution was clear and is approaching the formulation of T21 without the methyl-oxirane polymer with oxirane. This suggests that the level of CM may be as low as about 38% for the formulation of T21 without the methyl-oxirane polymer with oxirane. For the formulation T31 when the level of CM was increased from 38% to 39.2%, the solution was clear and is approaching the formulation of Example 27. This suggests that the minimum amount of CM is about 40% (that of Example 27) or that too much water addition made when solution turned opaque makes it difficult to reverse the cloudiness. For formulations with about 15% propylene glycol (T26 and T30), it appears that at least an additional 3% CM is needed to achieve a clear formulation, whereas for T31 an additional 2% CM was used.
This Example is presented to evaluate the partial or complete replacement of Citrus Mulse (CM) with Natural Mulse in four formulations (T25, T22, T23, and T24). The formulations and status are shown below in Table 19.
The data show that Natural Mulse alone does not work well. CM works well with or without methyl-oxirane polymer with oxirane or Natural Mulse. 15% propylene glycol in the formulation does not work well with 5% methyl-oxirane polymer with oxirane. For formulation T22 when the level of propylene glycol was increased from 14.9% to 18.8%, there was no appreciable change noted.
This Example is presented to evaluate EZ-Mulse as a replacement for Citrus Mulse. Formulation T15 along with its status is shown below in Table 20.
The data show that EZ-Mulse alone does not work well.
In the foregoing description, certain terms have been used for brevity, clarity and understanding, however, no unnecessary limitations are to be implied therefrom, because such terms are used for descriptive purposes and are intended to be broadly construed. Moreover, the descriptions and examples herein are by way of examples and the exemplary embodiment is not limited to the exact details shown and described.
In the following claims, any feature described as a means for performing a function shall be construed as encompassing any means known to those skilled in the art to be capable of performing the recited function, and shall not be limited to the features and structures shown herein or mere equivalents thereof. The description of the exemplary embodiment included in the Abstract included herewith shall not be deemed to limit the invention to features described therein.
Having described the features, discoveries and principles of the invention, the manner in which it is formulated and operated, and the advantages and useful results attained; the new and useful compositions, ingredients, combinations, systems, operations, methods and relationships are set forth in the appended claims.
| Number | Date | Country | |
|---|---|---|---|
| 61512017 | Jul 2011 | US |
